STOTEN-18500; No of Pages 12

Science of the Total Environment xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Review

A review on the use of membrane technology and fouling control for olive
mill wastewater treatment
Javier Miguel Ochando Pulido
University of Granada, Chemical Engineering Department, 18071 Granada, Spain

H I G H L I G H T S

Olive mill wastewater can be effectively treated through of membrane technology.

Different integrated membrane treatment processes are summarized and discussed.
Appropriate fouling inhibition methods should be set upstream membrane operation.
Feasible energetic and added-value compounds valorization of concentrate streams.
Final treated efuent compatible for reuse in irrigation can be achieved.

a r t i c l e i n f o a b s t r a c t

Article history: Olive mill efuents (OME) by-produced have signicantly increased in the last decades as a result of the boost
Received 15 August 2015 of the olive oil agro-industrial sector and due to the conversion into continuous operation centrifugation
Received in revised form 29 September 2015 technologies. In these efuents, the presence of phytotoxic recalcitrant pollutants makes them resistant to
Accepted 29 September 2015
biological degradation and thus inhibits the efciency of biological and conventional processes. Many reclama-
Available online xxxx
tion treatments as well as integrated processes for OME have already been proposed and developed but not
Keywords:
led to completely satisfactory and cost-effective results. Olive oil industries in its current status, typically small
Olive mill wastewater mills dispersed, cannot afford such high treatment costs. Furthermore, conventional treatments are not able
Microltration to abate the signicant dissolved monovalent and divalent ions concentration present in OME. Within this
Ultraltration framework, membrane technology offers high efciency and moderate investment and maintenance expenses.
Nanoltration Wastewater treatment by membrane technologies is growing in the recent years. This trend is owed to the
Reverse osmosis fact of the availability of new membrane materials, membrane designs, membrane module concepts and general
Membrane bioreactors know-how, which have promoted credibility among investors. However, fouling reduces the membrane
Wastewater reclamation
performances in time and leads to premature substitution of the membrane modules, and this is a problem of
cost efciency since wastewater treatment must imply low operating costs. Appropriate fouling inhibition
methods should assure this result, thus making membrane processes for wastewater stream treatment both
technically and economically feasible. In this paper, the treatment of the efuents by-produced in olive mills,
generally called olive mill wastewaters, will be addressed. Within this context, the state of the art of the different
pretreatments and integral membrane processes proposed up to today will be gathered and discussed, with an
insight in the problem of fouling.
2015 Elsevier B.V. All rights reserved.

1. Introduction
In the last decades, the efuents generated by olive oil industries,
commonly known as olive mills, have signicantly increased as a
result of the boost of the olive oil agro-industrial sector, also due to
the technological conversion into continuous operation centrifuga-
tion processes. The olive oil sector has represented since several
decades one of the most important industries in the Countries of
E-mail address: jmochandop@ugr.es.
the Mediterranean River Basin. In Spain, the main olive oil producer
with more than 45% of the total olive oil production worldwide, there
are more than 1700 olive mills currently authorized and operating.
More than 1,400,000 tons of olive oil were produced in Spain during
the 20132014 campaign, 70% of which were obtained in Andaluca
where there are 850 olive mills, which yielded a production of
1,022,000 tons of olive oil as well as 4,778,451 tons of table olives,
highlighting the provinces of Jan, with more than 515,000 tons of
olive oil and 2,229,000 tons of olives, Granada with 118,000 tons of
olive oil and 509,383 tons of olives, and Crdoba with 219,000 tons
of olive oil and 1,123,800 tons of olives.

http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
0048-9697/ 2015 Elsevier B.V. All rights reserved.

Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
2 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
The production of olive oil employs a very signicant number of
people and is one of the main industrial activities, as in other countries
of the Mediterranean Basin: Italy, Portugal, Greece and the Northern
African countries Syria, Algeria, Turkey, Morocco, Tunisia, Libya,
Lebanon, Egypt (Fig. 1). Other countries such as France, Serbia and
Montenegro, Macedonia, Cyprus, Turkey, Israel and Jordan also produce
a considerable annual olive oil yield (International Olive Oil Council,
IOOC, 20132014). Moreover, olive oil production is also rapidly becom-
ing an emergent agro-food industry in China and other countries such as
the USA, Australia and the Middle East. It is very worth highlighting the
case of China, which exhibits favorable edaphoclimatic conditions for
the growth of the olive trees, and is expected to develop a considerable
olive oil production potential in the near future. Hence, the treatment of
the olive mill efuents (OME) is already a task of global concern and is
not anymore a problem constrained to a specic region.
The technological change of olive oil production, with the introduc-
tion of continuous centrifugation processes in replacement of the an-
tique batch press methods, has ensured higher productivity, but have
led to a signicant increment of the efuents by-produced in these
industries (OME) as well. Currently, an average-sized modern olive oil
mill generates between 10 and 15 m3 daily of wastewater derived
from the centrifugation process, called olive mill wastewater (OMW),
together with 1 m3 of olive washing wastewater (OWW) per ton
of processed olives. This raises several millions cubic meters of OME
each year.
Whereas OWW is commonly composed of high concentration
of suspended solids (mainly peel, pulp, ground, branches and leaves
debris) derived from the washing procedure of the olive fruit, but low
concentration of dissolved organic matter depending on the water
ow exchange rate in the washing machines during the fruit cleaning
procedure usually below the standard limits for discharge on super-
cial suitable terrains; on the other hand, discharge of untreated OMW to
the ground elds and supercial waters bodies is currently prohibited
in Spain, whereas in Italy and Portugal as well as in other European
countries only partial discharge on suitable terrains is allowed. Straight
discharge of OMW has been reported by several authors to cause
strong odor nuisance, soil contamination, plants growth inhibition,
underground leaks, water body pollution and hindrance of self-
purication processes, as well as severe impacts to the aquatic
fauna and to the ecological status, due to the presence of bio-refractory
contaminants, including a wide variety of phenolic compounds, tannins,
fatty acids and organohalogenated pollutants (Danellakis et al., 2011;
Hodaifa et al., 2008, 2013a; Karaouzas et al., 2011; Martnez Nieto
et al., 2011a; Ntougias et al., 2013). Due to the presence of high
levels of refractory organic compounds, direct disposal of OMW to the
municipal sewage treatment plants is also prohibited.
In this scenario, the European Directive 2000/60/CE took the lead in
establishing the legal framework to confer utmost protection to water,
highlighting the use of regenerated wastewater. Moreover, European
Environmental Regulations will become more stringent in virtue of
Fig. 1. Olive oil production worldwide (International Olive Oil Council, IOOC 2014).
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
the H2020 Horizon (http://ec.europa.eu/programmes/horizon2020/).
Water scarcity specially concerns agricultural irrigation, which de-
mands more than 70% of the total water consumption worldwide
(Food and Agricultural Organization (FAO), 2003). However, there is a
big potential to use regenerated wastewater for irrigation purposes,
which would result in a solution with very positive environmental
and economic impacts.
Geographical dispersion of olive oil mills, as well as their small size
and the seasonality of olive oil production, are handicaps that have
typically made the management of OME quite cost-ineffective. Further-
more, the physico-chemical composition of OME is extremely variable
as it depends on several factors such as the type of olive oil extraction
process, the edaphoclimatic conditions of the region and cultivation
parameters, as well as the type, quality and maturity of the kind of
processed olives. OME typically exhibit intense violet-dark color,
acid pH, strong odor, considerable saline toxicity reected by
high electroconductivity values, and very heavy organic pollutants
load (Table 1).
In the continuous two-phase extraction process water injection
is only performed in the nal vertical centrifugation step, therefore
the volume of liquid efuent derived from the production process
(OMW-2) is reduced by one fth on average if compared to the amount
required for the three-phase system (Table 2). On the other hand, much
of the organic matter remains in the solid waste, which contains more
moisture than the pomace from the three-phase system (60 70% in
two-phase systems vs. 30 45% in three-phase ones, OMW-3) and
hence OMW-2 exhibits lower pollutants degree, too: the measured
chemical oxygen demand (COD) in OMW-2 is commonly in the range
416 g/L in contrast with up to 30200 g/L for OMW-3. Inorganic com-
pounds including chloride, sulfate and phosphoric salts of potassium,
calcium, iron, magnesium, sodium, copper and traces of other elements
are also common traits of OMW (Niaounakis and Halvadakis, 2006;
Paraskeva and Diamadopoulos, 2006).
A wide variety of stand-alone and integrated processes for the
treatment of OMW have already been proposed and developed but
have not yet led to completely satisfactory results, such as lagooning
or natural evaporation and thermal concentration (Annesini and
Gironi, 1991; Paraskeva and Diamadopoulos, 2006), composting
(Bouranis et al., 1995; Cegarra et al., 1996; Papadimitriou et al., 1997),
treatments with clay (Al-Malah et al., 2000) or with lime (Aktas et al.,
2001), physico-chemical procedures including coagulationocculation
(Martnez Nieto et al., 2011b; Sarika et al., 2005), electrocoagulation
(Inan et al., 2004; Tezcan n et al., 2006) and biosorption (Hodaifa
et al., 2013a; Martnez Nieto et al., 2010; Stasinakis et al., 2008),
advanced oxidation processes comprising ozonation (Caizares
et al., 2006, 2007 and Caizares et al., 2009), Fenton's reaction
(Hodaifa et al., 2013b) and photocatalysis (Chatzisymeon et al.,
2009; Sacco et al., 2012), electrochemical treatments (Inan et al.,
2004; Papastefanakis et al., 2010, Tezcan n et al., 2008) and hybrid
processes (Ammary, 2005; Beltran-Heredia et al., 2001; Graas et al.,
2010; Khou et al., 2006; La et al., 2009; Rizzo et al., 2008).
Various authors have noticed that common biological treatment
processes active sludge are not effective for the treatment of OMW
Table 1
Characteristics of the efuents of batch and continuous (three-phase and two-phase) olive
oil extraction processes.
Process Efuent COD, g/L BOD5, TSSs, pH EC, TPh,
g/L g/L mS/cm g/L
Olives cleaning OWW 0.82.2 0.31.5 818 5.56.6 2.53.0 00.1
Batch press OMW-P 130130 90100 1012 4.55.0 2.05.0 1.02.4
Three phase OMW-3 30200 545 535 3.55.5 2.07.9 0.37.5
Two phase OMW-2 416 0.86.0 27 3.56.0 1.52.5 0.11.0
COD: chemical oxygen demand; BOD5: biological oxygen demand; TSS: total suspended
solids; EC: electric conductivity; TPh: total phenols; OWW: olive washing wastewater;
OMW-P: press OMW; OMW-3: three-phase OMW; OMW-2: two-phase OMW.
 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
Table 2
Efuents owrates of continuous olive oil extraction processes (Mendoza et al., 1996).
Efuent, L/kg 3-Phase extraction 2-Phase extraction
Washing of olives (OWW) 0.06 0.05
Horizontal centrifuge 0.90 0 01
Vertical centrifuge 0.20 0.15
Cleaning 0.05 0.05
Total 1.21 0.25
(Fountoulakis et al., 2002; Garrido Hoyos et al., 2002; Paraskeva and
Diamadopoulos, 2006; Taccari and Ciani, 2011). On the other hand,
as reported by several researchers, OMW characteristics such as
the acidic pH, low alkalinity and low nitrogen content, as well as the
presence of lipidic and phenolic fractions, make this wastewater
potentially toxic for anaerobic treatments (Beltran-Heredia and Garcia,
2005; Marques, 2001; Sampaio et al., 2011; Tekin and Cokun, 2000).
However, as pointed by Sampaio et al. (2011), the high organic matter
concentration of OMW represents a very signicant energetic potential
to obtain biogas through anaerobiosis. In this regard, co-digestion of
OMW with other substrates, such as agro-livestock, has been pointed
as a feasible alternative (Gonalves et al., 2012a, 2012b; Kougias et al.,
2014; Sampaio et al., 2011). Otherwise, Scoma et al. (2013) proposed
an anaerobic acidogenic process with dephenolized OMW-3 under
mesophilic conditions in packed-bed biolm reactors inoculated with
an acclimated microbial consortium, attaining a signicant production
of a H2-rich biogas upon 1 day hydraulic retention times.
Sampaio et al. (2011) obtained good results in the treatment of
raw OMW-3 (100% v/v, without any pretreatment or correction) in an
up-ow anaerobic hybrid reactor. The treatment process was based on
efuents complementarity concept, that is, the inuent contained
a blend of the raw OMW-3 and a complementary substrate (piggery
efuent), such that the OMW-3 content was gradually increased
(0100%) or weekly load shocks were applied. As a result, the hybrid
microbial community became adapted to the unfavorable character-
istics of OMW. They obtained up to 3.73.8 m3 biogas m 3 day 1
containing 6364% CH4 as well as 8182% COD removal by applying
8 kg COD m 3 day 1 loads. At the end of the process, an efuent
with basic pH (8.1) and high alkalinity was obtained. Similarly,
Gonalves et al. (2012b) examined the performance of an anaerobic
hybrid reactor for the treatment of OMW-3 without water dilution,
chemical correction or any pretreatment. The strategy consisted in
mixing the raw OMW-3 with piggery efuent as complementary
feeding substrate, thus progressively increasing the OMW-3 volume
fraction (from 8% to 83%) in the feed mixture. The authors reported a
biogas production equal to 3.16 m3 m 3 day 1 at an organic loading
rate of 7.1 kg m 3 day 1 COD when the highest fraction of OME was
added to the inuent (83% volume fraction and 94% COD concentra-
tion fraction). The authors highlight the hybrid digester as a feasible
alternative to maximize the bioenergy recovery from OMW, offering
as advantages the prevention of excessive loss of biomass and its
capability to recover from accidental overloads. Moreover, the
proposed feeding strategies may be a potential solution for the
anaerobic treatment of OMW, especially in regions where these
co-substrates are available.
In addition, conventional physicochemical treatments are not effec-
tive for the removal of the signicant salinity of OMW, reected in high
electroconductivity (EC). These treatments are not able to abate the
high concentration of dissolved monovalent and divalent ions present
in these efuents, which present hazardous salinity levels according to
the guidelines established by the Food and Agricultural Organization
(F.A.O.) for irrigation uses (Table 3). One possible solution to attain com-
plete depuration of OMW can be coupling of anaerobic digestion with
electrochemical process (Gonalves et al., 2012a, 2012b). See Table 4.
Within this context, advanced separation technologies are a high
potential option in order to attempt the complete depuration of OMW.
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
3
Table 3
Water quality for irrigation and risk to soil as a function of its salinity (Food and
Agriculture Organization, FAO).
EC, dS/L Water quality Risk due to salinity
Excellent to good Low to mid
13 Good to marginal High
N3 Marginal to unacceptable Very high
In this regard, membrane technology offers compact modular nature,
high efciency and moderate investment and maintenance costs.
Membrane processes are becoming increasingly used in the recent
years in the purication of water and groundwater, in replacement of
many conventional separation processes, as well as in the reclamation
of wastewater streams of very diverse sources, such as those generated
by agro-industrial activities (Bdalo et al., 2003; Iaquinta and Stoller,
2009; Luo et al., 2012; Macedo et al., 2015; Ochando-Pulido et al.,
2012a, 2012b; Stoller and Chianese, 2006a, 2006b; Stoller and Bravi,
2010; Stoller, 2008, 2009, Stoller, 2011).
The availability of new membrane materials, designs, module con-
gurations and know-how has promoted credibility among investors.
However, fouling is a deleterious problem common to all membrane
processes. If irreversible, it reduces the membrane service lifetime dras-
tically. In any case, fouling alters the selectivity of the membrane and
depletes its productivity, making integrated membrane wastewater
treatment processes economically unfeasible (Bacchin et al., 2006;
Espinasse et al., 2002; Field and Pearce, 2011; Le-Clech et al., 2006;
Ochando-Pulido et al., 2012c; Stoller et al., 2012, 2013a, 2013b; Stoller
and Ochando-Pulido, 2012; Yiantsios and Karabelas, 2002).
In the present work, the state of the art of the different pretreat-
ments and integral membrane processes proposed up to today for
the reclamation and disposal of the efuents generated in olive
mills operating with batch-press and two-phase and three-phase
processes will be gathered and discussed, comprising microltration
(MF), ultraltration (UF), nanoltration (NF) and reverse osmosis
(RO), as well as membrane bioreactors (MBRs), with an insight in
the problem of fouling.
Fouling is a problem of cost efciency since wastewater treatment
must imply low operating costs. Appropriate fouling inhibition methods
should assure this result, thus making membrane processes for
the treatment of these wastewater streams both technically and
economically feasible.
2. Wastewater treatment by membranes: current framework
The use of membranes for the treatment of wastewater streams
appeared 30 years ago. However, at the beginning the technology was
not capable of maintaining the performances as a function of time,
mainly due to membrane fouling. The consequence was a lack of con-
dence in membrane technologies during the last two decades. The
recent availability of new membrane materials, membrane design
methods, module congurations and the improvement of the know-
how in general, and in particular on membrane fouling mechanisms,
has permitted membrane technologies gain credibility among engineers
and investors for wastewater treatment purposes. Moreover, the rapid
boost of wastewater volumes produced worldwide is opening a new
market for membranes, which have a signicant potential to take
the role as the core technology for these applications. In fact, today an
increasing number of municipal wastewater treatment facilities are
using membrane technologies, and this number is growing every year.
Membranes processes exhibit high selectivity values required to achieve
high water quality standards, are more cost-effective than other conven-
tional processes, require less area and can replace several unit treatment
processes by a single one.
In the past years, MF, UF, NF and RO membranes have been increas-
ingly implemented in water treatment processes such as groundwater
 ce
a-
f-
r-
u-
s-
d
n-
a-

4
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,

Table 4
Main research works on olive mill efuents treatment by membrane technologies.

Author/s Raw OME source Treatment Scale Process ow-scheme Used membrane Dynamic fouling-ux Achieved standards Results
process target characteristics behavior

Canepa et al. (1988) Batch or continuous Recycling and Pilot (continuous) (1) UF, (2) treatment Tubular UF (PS, 102 80% UF ux decline COD reduction (UF) up Final treated efuent
3-phase olive oil agricultural irrigation with adsorbing kPa, MWCO 20 kDa); after 20 h and nearly to 63%, 93% (RO) and showed 93% COD and
extraction + added-value polymers and (3) RO SW RO 70% after 15 h of RO 99% total 99% total dissolved
products recovery (polypiperazine-amide, solids removal upon
40 kPa) VRF equal to 6, reusable
for agricultural
irrigation
Borsani and Ferrando Batch or continuous Discharge on supercial Pilot (continuous) (1) Oil removal and TSS Tubular UF (PS, 10 bar, Not reported 50% COD load decrease Efuent compliance of
(1996) 3-phase olive oil waters settling, (2) UF, MWCO 30 kDa) after UF and up to 70% Italian standards for
extraction (3) permeate mix with after biological supercial water

J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx

sewage and treatment discharge, 150 m3/d
(4) double-stage average
biological treatment
Turano et al. (2002) Continuous 3-phase Pollution reduction + Lab (batch) (1) Centrifugation and Flat-sheet UF (PS, Above 80% ux decline 55% COD and 80% ashes Efuent COD (5 g O2/L)
olive oil extraction selective separation of (2) UF of centrifuge MWCO 17 kDa) after 30 min, 83% initial and TSS reductions after still high for European
added-value products supernatant ux recovery after centrifugation, 90% nal legislation; complete fat
from OMW cleaning COD abatement rejection, separated from
salts, sugars and
polyphenols, contained in
permeate stream
Paraskeva et al. (2007) Continuous 3-phase Fractionation of value Pilot (batch) (1) 80 m Multichannel UF Fouling data not 90% lipids and 50% Efuent suitable for
olive oil extraction by-products to and polypropylene lter, (zirconia, 100 nm, reported; 100120 L/h phenols separated by irrigation or aquatic
efuent reclamation (2) UF, (3) NF and 12.25 bar); polymeric within NF, 3032 L/h UF; 95% phenols receptors
(4) RO SW NF (200 Da, 20 with RO removal
bar) and SW RO
(100 Da, 40 bar)
Russo (2007) Continuous 3-phase Selective recovery of Pilot (batch) (1) MF, (2) UF and MF ceramic (ZO, 0.8 and High ux drop and RO 99.9% nitrogen RO retentate enriched in
olive oil extraction added-value products (3) RO 0.45 m) and PES SW incomplete membranes substances, sugar and LMW polyphenols for
from OVW (500 kDa); UF SW permeability restore polyphenol rejection food, pharmaceutical or
polymeric (80, 20 and 6 after cleaning and 83%99% with cosmetic industries; MF
kDa; PS or PES) and procedure respect to ionic species and UF retentates as
ceramic (ZO, 1 kDa); fertilizers or for biogas
composite SW RO yield
Garcia-Castello et al. Continuous 3-phase OVW reclamation + Pilot (batch) (1) MF, (2) NF and MF ceramic (Al2O3, 200 35% MF initial ux drop MF achieved 91% and NF permeate stream
(2010) olive oil extraction selective separation of (3) OD or VMD nm, 0.72 1 bar); SW and incomplete restore 26% TSS and TOC containing polyphenolic
added-value products NF (hydrophobic PES, after cleaning (106 reduction; NF removed compounds for food,
578 Da, 8 bar) L/hm2 bar); 35% NF 63% TOC and TC cosmetic or
initial ux (4.68 L/hm2) reduction in MF pharmaceutical sectors;
drop above VRF = 3 permeate 0.5 g/L free LMW
polyphenols, with 56%
hydroxytyrosol,
obtained by treating the
NF permeate by OD
Stoller et al. Continuous 3-phase OVW and OVW for Pilot (batch) (1) pretreatment Composite SW MF (300 Lowest ux drops MF Overall COD abatement Italian standards for
(20062013) olive oil extraction sewers discharge or among nm), UF (2 nm), NF 17.318.9%, UF 23.1%, NF 98.899.4% municipal sewer system
irrigation + fouling occulation/UV-TiO 2 (0.5 nm) and RO (b0.1 18.5%, RO 22.923.7%; discharge (COD values
inhibition and photocatalysis/aerobic nm); operating below reversible fouling below 500 mg/L) achieved
prediction digestion/MF, critical pressure removed after cleaning
followed by (2) UF +
NF + RO
 Akdemir & Ozer (2009) Continuous 3-phase Satisfy standards for Lab (batch) (1) pH adjustment, Flat-sheet UF Highest ux 25.9 L/hm2 COD, TOC and SS Efuent COD, TOC and SS
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,

olive oil extraction wastewater discharge (2) cartridge ltration (polyvinylidine-- at 4 bar affected by removal ratios 92.3%, 6.4 g O2/L, 2.5 g/L, 320
to sewers and (3) UF diuoride, 30 kDa and fouling; 1 bar safest 92.7%, 97.1% mg/L; although sewers
another Ultralic 100 operating pressure discharge standards not
kDa, 1 bar) obtained, further
investigations on posed
pretreatment should be
considered
Ochando et al. (2012) Continuous 2-phase OMW reclamation for Pilot (1) Fenton-like Composite PA/PS at High and stable 100% TSS, phenols and Efuent COD below 5 mg
olive oil extraction sewers discharge or (semi-continuous) oxidation, RO permeate ux upon iron removal, 99.4% and O2/L, within standards for
reuse in process (2) occulation- recirculating above 10% 98.2% COD and reuse in olives washing
sedimentation, permeate conductivity machines
(3) biosorption and
(4) RO
Ochando-Pulido et al. Continuous 2-phase OMW reclamation for Pilot (1) UF followed by Composite PA/PS SW 13.2 L/hm2 for UF 10.5 90.5% UF and 82.8 % NF Final treated efuent
(2014) olive oil extraction sewers discharge or (semi-continuous) (2) NF and (3) RO L/hm2 for NF COD removal compliant with standards
reuse in process steady-state for reuse in olive washing
performances machines
Zirehpour et al. (2012) Continuous 3-phase OMW reclamation for Pilot (continuous) MFUFNF membrane MF (50, 5 and 0.2 m), 34.1 L/hm2 for UF and 51.2% UF COD rejection 98.8% COD removal in

J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx

olive oil extraction irrigation reuse system UF (10035 kDa) and 9.4 L/hm2 for NF and 64% NF salt whole integrated system,
purposes NF (450150 Da) rejection (VRF = 4) with applied pressure for
NF lower (5 bar) in
comparison with other
studies
Coskun et al. (2010) Continuous 3-phase OMW reclamation for Pilot (continuous) (1) Centrifugation, UF cellulose and Permeate uxes up to COD removal 59.479.2 Even though these values
olive oil extraction sewers discharge or (2) UF, (3) NF and polyethersulfone, NF 21.228.3 L/m2 h for NF % for NF membranes, of conductivities were
reuse in process (4) RO polyamide and RO membranes and whereas 96.2 %96.3 % within acceptable
polyamide 12.615.5 L/m2 h for RO for RO membranes standards for drinking
membranes waters, higher efuent
COD values were observed,
due to fermentation
products during storage of
the raw efuent
El-Abbassi et al. (2011) Press-based olive oil OMW reclamation and Lab (stirred batch) Micellar enhance UF PVDF at-sheet UF Initial uxes from 25.7 Rejection efciency of Proposed MEUF process
extraction process added-value process (MEUF) membranes to 44.5 L/hm2 h under polyphenolic provided a slightly colored
compounds recovery transmembrane compounds became permeate (~88% lower
pressures of 3.54.5 bar increased up to 74%. darkness), which
presented 95.6% less
chemical oxygen demand
(COD)
Cassano et al. (2013) Continuous 3-phase OMW reclamation and Lab (continuous) (1) Two UF membranes PVDF hollow ber UF, Initial UF ux 12 L/m2 h RO permeate produced NF permeate produced at
olive oil extraction added-value in series, (2) followed composite uoro upon VRF of 3, at 40 bar characterized 5 bar is depleted in low
compounds recovery by ND polymer at-sheet UF, decreased rapidly (50 by TOC and phenols MW polyphenols and its
SW polymeric TFC NF min) to 2 L/m2 h; initial contents of 117 and 2.4 TOC value is 95 mg/L.
NF ux 13.75 L/m2 h mg/L, respectively
decreased to 3 L/m2 h
Dhaouadi & Marrot Continuous 3-phase OMW reclamation for Lab (continuous) MBR fed with Monochannel ceramic Stable permeate ux of COD abatement 5881% Permeate with zero
(2010) olive oil extraction irrigation or discharge decreasingly diluted MF membrane around 100 L/hm2 suspended solids and
OMW almost no phenolic
compounds
Conidi et al. (2014) Continuous 3-phase OMW reclamation and Lab (continuous) (1) MF, (2) UF and Lab (continuous) Flat-sheet MF (CA, nylon, Steady-state ux Maximum oleuropein
olive oil extraction production of (3) MBR PVDF), at-sheet UF reached in MBMR, conversion 45.7% and
phytotherapics (regenerated cellulose), thanks to pretreatment reaction rate 2 104
hollow ber UF (PS) mmol/min cm

SW: spiral-wound; LMW: low molecular weight; OD: osmotic distillation; VMD: vacuum membrane distillation; CA: cellulose acetate; PES: polyethersulfone; PS: polysulfone; PA: polyamide; PVDF: polyvinylideneuoride; ZO: zirconium oxide; VRF:
volume recovery factor.

5
6 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
water (Van der Bruggen et al., 2001; Van der Bruggen and
Vandecasteele, 2003), desalination of brackish water and seawater
(Paugam et al., 2004; Tu et al., 2010) and decontamination of
wastewater of diverse nature including urban wastewater (Lpez
et al., 2006), coking (Korzenowski et al., 2011; Yin et al., 2011),
carwash (Boussu et al., 2007), nuclear power (Epimakhov et al.,
2004), power engineering (Samodurov et al., 2006) steel industry
(Jae-Wook Lee et al., 2006), textile and tannery (Ellouze et al.,
2012; Stoller et al., 2013b), pulp and paper (Mnttri and Nystrm,
2000; Pizzichini et al., 2005), pharmaceutical (Wei et al., 2010) and
agro-food industries such as dairy (Luo et al., 2012; Macedo et al.,
2015), beverage (Agana et al., 2013), winery (Ioannou et al., 2013;
Giacobbo et al., 2013), tomato (Iaquinta and Stoller, 2009) and
olive oil (Stoller and Chianese, 2006a, 2006b; Stoller et al., 2013a;
Ochando-Pulido et al., 2012a, 2012d), among others. In particular
for wastewater applications, membranes are currently being used
as tertiary advanced treatment for removal of dissolved species
such as non-biodegradable organic pollutants, phosphorus, nitrogen
compounds, colloidal and suspended solids, and human pathogens,
including bacteria, protozoan cysts and viruses.
In order to successfully design a membrane process for a specic
application at industrial scale, the constancy of the performances is
mandatory. The difculty in achieving this task is given by the fouling
phenomena occurring dynamically over the membrane during opera-
tion, which reduce the membrane performances as a function of time.
The rst phenomenon that triggers over the membrane surface is
concentration polarization, caused by the increasing concentration of
solutes near the membrane boundary region. It may also reach such
high values to enable the formation of gel layers. In this state, the solutes
will deposit over the membrane, and cleaning may be difcult although
not impossible (reversible). If the concentration within the gel layer
exceeds solubility concentration values, a solid starts to precipitate
and stick to the membrane surface. This impermeable layer represents
irreversible fouling and cannot be washed away anymore (see Fig. 2).
Membrane fouling is complex, and may involve membrane pore
blocking, plugging and clogging, chemical degradation and/or cake for-
mation on the membrane surface caused by microorganisms as well as
organic and inorganic material (Le-Clech et al., 2006; Cheryan, 1998).
Nevertheless, the result is always a reduction of the membrane perfor-
mances in terms of permeability, selectivity and longevity. In the past,
fouling has sensibly compromised the reliability of membrane technol-
ogy. This trend is still actual, since proper membrane process design
can be a difcult task to accomplish when fouling is present and must
be faced (Ho and Sirkar, 1992). Fouling leads to a reduction of the
Fig. 2. Resistances-in-series occurring on the membrane.
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
membrane productivity and causes a sensible reduction of the mem-
brane module service lifetime, multiplying the operating costs up to
1020 times. The presence of fouling, and the consequent reduction
of permeate uxes as a function of time, forces the engineers to over-
design the membrane plant in order to guarantee the conduction of
the process for a certain period of time at or above the permeate project
values (Saad, 2005).
Belfort et al. and Field et al. started to study the experimental and
theoretical behavior of fouling in MF and UF membranes, respectively
(Belfort et al., 1994; Field and Aimar, 1993). The rst theoretical
model giving some explanation on membrane transport phenomena
of colloidal particles was proposed by the research group of Bacchin
et al. (1996); Field et al. (1995) and Mnttri and Nystrm, 2000.
Parallel to this, the existence of different fouling typologies was tried
to be formerly explained by works published by Bacchin et al. and
Ognier et al., based on the assumption of possible local conditions trig-
gering different liquid/gel phases over the membrane layer and in the
membrane pores due to the concentration proles by polarization
(Ognier et al., 2004; Bacchin et al., 2006).
The feed stream composition is the main responsible of ever chang-
ing ux values, and this is especially true for agricultural wastewater
streams treatment by membranes, since the entering feedstock compo-
sition is not constant during the campaign. Furthermore, the use of
batch membrane processes in order to limit the amount of required
membrane area, and thus saving investment costs, leads to sensible
feedstock changes during operation.
In this regard, direct treatment by membranes of raw efuents has
been reported to lead to rapid emergence of membrane fouling
(Aimar and Bacchin, 2010; Le-Clech et al., 2006; Ochando-Pulido et al.,
2012c; Stoller and Bravi, 2010; Stoller, 2011; Vyas et al., 2002).
Appropriate fouling inhibition methods should be designed upstream
the membrane operation, in order to make the membrane processes
for wastewater treatment technically and economically feasible.
Hereafter, the different integrated membrane treatment processes
of the efuents by-produced in olive mills by membranes will be sum-
marized and discussed, with a focus on the appropriate pretreatments
to make the membrane operation performance stable and cost-efcient.
3. OMW treatment by MF, UF, NF and RO membranes
The biggest technical drawback for the implementation of
membrane technologies in wastewater treatment plants is the high
fouling potential. Membrane fouling mainly caused by colloids,
soluble organic compounds, and microorganisms increases the
feed pressure and obliges to frequent plant shut-downs for mem-
brane cleaning procedures. In this regard, OME contain high concen-
trations of a wide range of solutes in the form of suspended solids
and colloidal particles which are all very prone to cause membrane
fouling, such as organic pollutants, as well as inorganic matter that
may also lead to deleterious scaling problems.
Concerning this, properly-tailored pretreatment processes are
required in order to avoid high fouling rates, which would rapidly
lead to zero ux conditions if no pretreatment is conducted on the
raw efuent upstream the membrane operation.
Canepa et al. (1988) proposed an incipient treatment for three-
phase OMW based on an integrated membranes and adsorption process
at pilot scale. The treatment process comprised UF with polysulfone
membranes, after which the UF permeate stream was treated with
adsorbing polymers. The UF pilot plant consisted of four modules in
series containing three tubular membranes each, operating at 102 kPa.
The resins eluate was nally conducted to treatment with two RO
polypiperazine-amide membranes in series, operating at 40,102 kPa.
The UF membrane achieved up to 63% COD rejection and a nal volume
reduction factor (VRF) equal to 11. The resin bed showed good retention
of polyphenolic compounds, permitting the treatment of up to 3000 L
until saturation was reached. The COD rejection and total dissolved
 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
solids removal in the nal RO treated efuent, up to 93% and 99% upon a
VRF of 6, permitted reuse it for recycling and agricultural irrigation pur-
poses. However, the performances of the used UF and RO membranes
became rapidly and irreversibly depleted, due to quick and strong
form of membrane fouling as a result of the absence of proper
membrane pretreatment methods.
An alternative membrane-based process for three-phase OMW
treatment was addressed by Borsani and Ferrando (1996) at a pilot
scale. The proposed process comprised oil removal and suspended
solids settling as pretreatments upstream the tangential UF membrane
process. A nal step was set consisting in double-stage biological treat-
ment of the UF permeate stream mixed with sewage (1:16 owrate
ratio). The UF process comprised 220 modules subdivided in 3 batteries,
each module composed of 18 tubular membranes (polysulfone,
molecular weight cut-off MWCO equal to 30 kDa) and was carried
out at 10 bar. At the outlet of the second stage of the nal biological
treatment, nal average BOD5 and COD reported abatement was up to
6570%. As a result, the nal treated stream exiting the plant complied
with Italian standard limits for discharge in supercial waters, providing
a daily treatment capability up to 150 m3.
Turano et al. (2002) proposed a physical pretreatment consisting
in centrifugation of the raw OMW, highlighting its simplicity and
mechanical operation, without need of addition of chemicals. The
integral process consisted in a combined centrifugation-UF process for
the treatment of OMW from three-phase centrifugation-based olive
mills. The centrifugation pretreatment achieved complete suspended
solids removal, then the supernatant was conducted to UF (polysulfone,
MWCO 17 kDa). Up to 55% COD reduction was achieved after the pro-
posed centrifugation pretreatment, whereas 80% removal of suspended
solids concentration and 90% for COD was achieved at the outlet of the
integrated process.
They analyzed the permeation efciency by the cake-ltration
model as a function of several parameters comprising the importance
of the pretreatment, the effects of localized turbulence promoted by
the UF module geometry, and of the main operating variables: temper-
ature (30 C), transmembrane pressure PTM (0.5-3 bar) and owrate.
They also fullled a rheological characterization of the waste. Higher
steady state ux was also ensured for the pretreated OMW and much
smoother efciency decay to its stationary value, enabling longer work-
ing cycles and less frequent plant shutdowns for membrane cleaning.
Steady state values showed that centrifuged wastewater permeate
ux was about 13 times higher than raw OMW.
However, fouling still remained a severe problem even in presence
of this pretreatment, evident not only from the ux decay but also
from the decrease of the steady state UF efciency upon increasing
operating pressures, due to the increase of the transport resistance.
After each experiment, a combined alkaline and acid cleaning cycle
was carried out over the membrane, severely fouled by organic com-
pounds and minerals present in OMW. Performing that standard
cleaning procedure, about 83% of the initial permeability could be
recovered when ultraltering pretreated OMW, while only 37% was
restored when ultraltering the raw wastewater. They attributed
membrane fouling to the oil phase enhancing agglomeration of
macromolecules (suspended solids, ashes, organic particles, etc.),
blocking the membrane pores and thus causing a steep permeate
ux drop (more than 95% after the rst 5 min) when no pretreat-
ment was used and a smoother one (7080% after 30 min) when a
great part of the suspended solids had been removed.
These results highlight the key importance of tailored and cost-
effective pretreatments for OMW management by membranes. Fouling
mitigation constitutes one of the main challenges of membrane technol-
ogy, as it involves operating and energy costs increments as well as
frequent membrane chemical cleanings and shut-downs, thus soaring
the consumption of cleaning reagents and causing costly process
interruptions. What is more, irreversible fouling leads to irretrievable
membrane life shortage. Dissolved and suspended organic matter
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
7
associated to OMW, such as polysaccharides and proteins, also
constitute a breeding ground for microbiological activity enhanc-
ing biofouling. In addition to colloidal particles and sparingly solu-
ble salts, they can also lead to accumulation of insoluble matter,
pore plugging and blocking, scale formation and cake-enhanced
concentration polarization.
Stoller and Chianese (2006a,b) studied the purication of the waste-
water stream generated in the olive washing wastewater (OWW) pro-
cedure, to comply with discharge standards in municipal sewers. In
contrast with OMW, this efuent presents moderate organic pollutants
load, but high concentration of suspended solids. Thereof, the authors
proposed a treatment process comprising an initial solid/liquid (S/L)
separation stage, followed by batch UF and NF in series (thin-lm com-
posite spiral-wound membranes). As S/L separation operation they
studied the use of coagulationocculation with polyelectrolytes:
aluminum sulfate (AS) or aluminum hydroxide (AH). The two pretreat-
ment processes performed similarly with regard to COD and BOD5
rejection efciencies, but higher productivity was observed in the
downstream membranes-in-series process after occulation with AS.
In a following research work, Stoller and Bravi (2010) applied the
same coagulantocculants to pretreat three-phase OMW before
batch MF, UF and NF membranes in sequence, and a nal RO step.
In addition, they examined two other pretreatment processes:
photocatalysis (PC) with titanium dioxide anatase nano-powders
under UV light irradiation, and aerobic digestion (AD). To sum up,
all pretreatment processes successfully tested enabled a nal RO
permeate with COD equal to 456 mg/L, 242 mg/L and 385 mg/L
for AS, BIO + AS and PC, respectively, complying with irrigation
quality standards.
However, UV/TiO2 photocatalysis performance was found as the
most efcient, with the highest membrane productivity in the shortest
residence time (24 h). Coagulationocculation residence time was
72 h for both coagulantocculants examined. A signicant reduction
of polyphenols and nal dry matter was attained with both coagulants,
but with AH the process had to be stopped at the UF step since
cost-sustainable permeate ow rates were not observed due to quick
fouling build-up on the membrane. Otherwise, a much longer residence
time equal to 7 days was needed for biodigestion.
In conclusion, a non-linear relationship between the stationary ux
and the pore-blocking particle density was remarked by these authors.
Pretreatment with AS led to higher permeate uxes due to minor
fouling issues. Similarly to the pretreatment with AH occurred after
AD, presumably owed to the fact that the residual biomass may give
rise to particles of dimension close to the MF pores' mean diameter,
being therefore discarded also due to the much longer residence time
(7 days), despite the fact of the comparable COD reduction achieved.
AD after coagulationocculation with AS was also evaluated, but the
COD reduction, even if higher, was not sufcient to compensate for
the critical ux decrease due to pore-blocking particles. AD was sug-
gested only in combination with coagulation (mediumhigh critical
ux values on all membranes, overall COD reduction equal to 98.6%),
since without any coagulant and the elimination of the bioocks
plugging of the MF membrane seemed not avoidable.
In light of the obtained results with OWW and OMW, Stoller (2009,
2011) underlined the key importance of the adequate pretreatment and
highlighted that higher pollutants reductions in the raw efuent, e.g. in
the COD or EC values, do not necessarily guarantee the most suitability
of the pretreatment procedure. The fact that the pretreatment brings off
pollutants particle size (dp) shift far away from that of the membrane
pores (Dp) is of relevant importance to further enhance better and
sustainable ux values.
In another research work with three-phase OMW, Akdemir and Ozer
(2009) proposed a membrane upstream pretreatment process based on
pH adjustment (acidic or alkaline) and cartridge ltration (20 m), with
the goal of complying with Turkish standards for wastewater discharge
into sewers. The authors compared the performance of two different
8 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
polymeric UF membranes, one of polyvinylidine-diuoride (with a
MWCO of 30 kDa) and the other an Ultralic membrane with a
MWCO of 100 kDa.
In detail, the pretreatment reached 63% COD removal. Finally, the
concentrations in the stream exiting the proposed treatment procedure
were equal to 6.4 g/L COD, 2.5 g/L TOC, 320 mg/L SS and 270 mg/L oil
and grease, corresponding to removal ratios of 92.3%, 92.7%, 97.1% and
98.9%, respectively. Moreover, an optimum transmembrane pressure
equal to 1 bar was reported as the safest operating pressure against
fouling issues. However, the pursued compliance with Turkish stan-
dards for wastewater discharge to sewers was not achieved, and further
investigations on the given pretreatment should be considered.
Coskun et al. (2010) investigated the treatment of three-phase
OMW previously centrifuged, then ltered via UF membranes followed
by NF, and nally RO membranes. The observed permeate uxes
reached values of up to 21.2-28.3L/m2 h for the NF membranes
whereas 12.615.5 L/m2 h for the RO membranes, respectively. The
maximum COD removal efciencies obtained at 10 bar ranged from
59.4 79.2% for the NF membranes, whereas between 96.2% and 96.3%
for the RO membranes, respectively. For the selected RO membranes,
the conductivity removal efciencies obtained at 25 bar ranged
between 93.2% and 94.8%. Nevertheless, these authors did not
address or report the effect of fouling on the steady-state permeate
ux performance and rejection/selectivity of the used membranes.
Zirehpour et al. (2012) examined an integrated MFUFNF mem-
brane system for the purication of three-phase OMW. The efuent
was pre-ltered by three-step MF in series, with nominal pore sizes of
50, 5 and 0.2 m, in concentration mode, subsequently followed by
two and three UF and NF membranes, respectively. However, the MF
membrane showed determinant fouling problems, very common in
MF membranes. Otherwise, the commercial UF membrane tested
provided higher permeate ux than the lab-made one, but the antifoul-
ing properties and rejection efciency of the latter was signicantly
better. A specic arrangement of the integrated membrane system
was concluded to be the UF membrane followed by two-step NF mem-
branes in series, the rst NF step providing high ux while the second
one providing high rejection.
It is very worth pointing that the studies available in the scientic
literature up to the moment report mainly membrane treatment pro-
cesses for OMW exiting olive mills operating with the three-phase
olive oil production technology, but very few membrane studies on
OMW generated by olive factories working with the two-phase extrac-
tion technology can be found. Also, the existing research works are
focused principally on the use of UF and NF membranes, yet there is a
gap of knowledge on RO purication of OMW.
Ochando-Pulido et al. (2012a, 2012b) studied the reclamation
of two-phase OMW by RO on a bench-scale, to achieve the quality to
recirculate the nal efuent to the olives washing machines in the
manufacture process to nally close the loop. The raw OMW was previ-
ously subjected to an advanced oxidation process (AOP) based on ho-
mogeneous Fenton-like reaction (Martnez Nieto et al., 2008, 2011a).
This AOP achieved high abatement of pesticides as well as polyphenols
and tannins besides other organic recalcitrant contaminants associated
to OMW. These compounds are resistant to biological degradation and
phytotoxic, and have also demonstrated to develop fouling on the mem-
branes (Lee et al., 2006). The authors reported that high and stable per-
meate uxes were yielded by the RO membrane unit upon recirculation
of a fraction of the permeate stream to the bulk tank. Under those con-
ditions, 100% suspended solids, phenols and iron removal was achieved,
in addition to 99.4% and 98.2% overall COD and conductivity rejection
efciencies, respectively.
On the other hand, Ochando-Pulido et al. (2014) studied a batch
membranes-in-series processes, in detail UF followed by NF and RO,
for the reclamation of two-phase olive mill wastewater (OMW2).
In this work, a pH-T occulation process followed by photocatalysis
with ferromagnetic-core titanium dioxide under ultraviolet irradiation
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
(UV/TiO2) was examined as pretreatment. The adoption of this treat-
ment sequence helped reducing signicantly the required membrane
area, 104.6 m2 and 81.4 m2 for the UF and NF membranes, respectively,
leading to a limited need of overdesign of the membrane plant. In addi-
tion, the use of the applied UV/TiO2 photocatalysis process enhanced
the productivity and longevity of both membranes, permitted achieving
a nal treated efuent compatible for irrigation purposes.
In another study, Ochando-Pulido et al. (2015) proposed a different
integrated batch UF and NF membranes-in-series process for the simul-
taneous treatment of the two main efuents generated in olive mills
operating with the two-phase technology, in particular wastewater de-
rived from the washing of the olives (OWW) and from the olive
oil washing during the vertical centrifugation (OMW). Beforehand,
the raw efuent, that is, 1:1 v/v mixture of OWW and OMW, called
OWMW2, was pretreated by pH-temperature occulation followed by
photocatalysis with TiO2 nanoparticles under UV irradiation. Signicant
and stable uxes were observed on both UF and NF membranes, 15.5
and 22.2 L h1 m2, respectively. Finally, the treatment line just com-
prising UF preceded by pH-T occulation and UV/TiO2 photocatalysis
provided an efuent compatible for irrigation and permitted reducing
considerably the membrane plant dimension.
In addition to these studies, some authors have also tried to
extract polyphenols, sugars and other added-value compounds
contained in this wastewater by concentration with membranes, in
order to counterbalance the treatment process costs. Notwithstanding,
in all these studies it can be noticed that membrane fouling plays an
important role.
Canepa et al. (1988) early proposed this possibility. Later on, Turano
et al. (2002) reported complete separation of fats, rejected by the UF
membrane, from salts, sugars and polyphenols, contained in the perme-
ate stream. However, despite the relevant COD reduction, the organic
matter concentration in the permeate was still too high, containing
polyphenols ranging from 0.2 to 0.3 g/L depending on the feed concen-
tration, sugars from 2 to 12 g/L and mineral salts ranging from 3 to 8 g/L.
They suggested converting the obtained polyphenolic fraction stream
either by means of enzymes immobilized in a membrane bioreactor
(Edwards et al., 1999; Durn and Esposito, 2000; Calabr et al., 2002),
thus reducing the permeate polluting load, or recovering them due to
their high antioxidant and radical scavenging properties (Rice-Evans
et al., 1996; Dreosti, 2000).
Similarly, Paraskeva et al. (2007) investigated the treatment and
complete fractionation of OMW coming from a three-phase olive oil
mill in Greece, using a combination of different membrane processes:
UF followed by NF and/or RO in batch mode. Prior to UF, screening
with an 80 m polypropylene lter was performed to remove
suspended solids. The UF membrane (ceramic zirconia, mean pore
size 100 nm in multichannel conguration) was operated upon a
recovery ratio xed between 8090% of the initial OMW volume,
operating temperature 1535 C and PTM between 1.0 and 2.25 bar.
The UF membrane accomplished the separation of high molecular
weight solutes including suspended solids, as well as the condensa-
tion of solid, fat, lipid components (~ 90%) and a large amount of
phenolic compounds (~ 50%).
Polymeric membranes in spiral wound conguration were used
for either NF (200 Da MWCO) or RO (100 Da MWCO) tests, in order
to further treat the UF permeate. In NF tests, the temperature was
maintained at 20 C and 20 bar optimum PTM, permitting yielding a
permeate owrate between 100120 L/h. Following the NF step,
phenolic compounds were removed to an extent above 95% of
the initial value, and better efciency was achieved by applying
RO after NF, which enabled a signicant conductivity, salinity and
turbidity reduction and about 30 L/h permeate owrate. Best perfor-
mances were found at 35 C and high-pressure values (PTM = 40 bar),
which allowed reaching a turbidity value of 14 NTU and a decrease of
up to 98.95% of the raw water conductivity, with a recovery between
7580% of the initial OMW volume.
 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
In the same line, other researchers have as well pin-pointed for the
potentiality of integrated membrane processes in recovering polyphe-
nols and other added-value organic compounds from these efuents.
Russo (2007) studied the reclamation of OMW by preliminary MF
followed by two-stepped UF (6 kDa followed by 1 kDa membranes)
and nal RO operation. Best productivities were 50 L/hm2 for VRF
equal to 3 for the ceramic MF membrane, whereas 1015 L/hm2
for UF with polymeric membranes of the MF permeate and up to
35 L/hm2 when ulfraltering the UF permeate with 1 kDa ceramic
membranes. Finally, 2025 L/hm2 were yielded by the RO membrane.
The author reported high concentration of low molecular weight
(LMW) polyphenols in the MF permeate, 76% being hydroxytyrosol.
Finally, the RO retentate contained enriched and puried LMW
polyphenols.
Garcia-Castello et al. (2010) proposed a treatment method compris-
ing MF, NF and nally vacuum membrane distillation (VMD) or osmotic
distillation (OD). MF ensured 91% and 26% reduction of suspended
solids and total organic carbon (TOC), respectively, as well as 78%
recovery of the initial content of polyphenols in the permeate stream.
Subsequently, NF achieved the recovery of most polyphenols in the
permeate, which was enriched by ulterior treatment by osmotic distilla-
tion (OD) or vacuum membrane distillation (VMD). A solution contain-
ing about 0.5 g/L of free LMW polyphenols, with hydroxytyrosol
representing 56% of the total, was produced by using calcium chloride
dihydrate solution as brine.
Notwithstanding, fouling on the membranes was evidenced
throughout the whole proposed treatment process. A very deep
and prompt permeate ux decline (35%) was observed in all MF
experimental runs. Furthermore, the initial permeability could not
be restored after the cleaning procedure, thus the permeate ux
was noticed to decay progressively after each operational cycle due
to irreversible fouling phenomena taking place on the membrane.
The polymeric 500 kDa MF membrane suffered more than 70% quick
permeate ux drop without reaching steady state and just 40% of the
initial permeability could be recovered after the cleaning protocol.
Russo (2007) also reported MF as critical due to severe fouling and
difculties in the cleaning procedure, and warned of the necessity of
an adequate pretreatment. UF membranes suffered as well from very
severe fouling problems, and only 80% of the initial UF permeability
could be restored after the cleaning procedure. For NF operation,
besides, important initial permeate ux (4.68 L/m2 h) decay occurred
(35%) for VRF above 3.
El-Abbassi et al. (2011) examined the efciency of micellar
enhanced UF (MEUF) with a hydrophobic polyvinylidene uoride
(PVDF) membrane, for reclamation together with removal and concen-
tration of polyphenolic compounds from three-phase OMW. They used
an anionic surfactant (sodium dodecyl sulfate salt, SDS) and investigat-
ed the effects given by the secondary membrane resistance created by
SDS molecules. The initial uxes of OMW processing by the proposed
MEUF process ranged from 25.7 to 44.5 L/hm2 h under transmembrane
pressures of 3.5 to 4.5 bar, respectively, and the rejection efciency
towards polyphenolic compounds became increased up to 74%.
Moreover, the proposed MEUF process provided a slightly colored
permeate (about 88% lower darkness), which presented 95.6% less
chemical oxygen demand (COD).
Cassano et al. (2011, 2013) evaluated the potential of an integrated
system comprising two UF membranes followed by nal NF in sequence.
Three different fractions were obtained: a concentrated stream from
the retentate of both UF membrane processes, containing high mo-
lecular weight organic substances, which depleted of polyphenolic
compounds may be subjected to an anaerobic digestion for biogas
production; another concentrated stream derived from the NF
retentate, enriched in LMW polyphenolic compounds suitable for
cosmetic, food and pharmaceutical industries as liquid, frozen,
dried or lyophilized formulations; and a nal treated water stream
(NF permeate), apt to be reused as process water or in the integrated
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
9
membrane system as membrane cleaning solution. However, only
87% ux could be recovered after cleaning, revealing deleterious
irreversible fouling build-up on the membrane.
As it can be seen, interesting added-value compounds contained in
OMW may be recovered, with the aid of concentration by membranes,
in order to counterbalance the wastewater treatment process costs.
However, further investigation is still to be done in order to compre-
hend, modelize, minimize and control the fouling problems associated.
4. The use of membrane bioreactors (MBRs) for OMW reclamation
In the recent years, the possibility of using membrane bioreactors
(MBRs) for the treatment and reclamation of OMW has been reported,
but very few studies are still available and much more information is
still required.
The feasibility of the use of membrane bioreactors (MBRs) for the
treatment of OMW was examined by Dhaouadi and Marrot (2010).
These authors used an external ceramic UF membrane bioreactor with
0.1 m MWCO. The experimental study was carried out with various
diluted OMW solutions continuously fed to the reactor in order to
permit the biomass to become gradually acclimated. The biomass was
previously adapted to phenol, being highlighted by the authors the
fact of its importance as it permits the microorganisms possess the
enzymatic material necessary to degrade the phenolic compounds,
thus producing a new population which is adapted to this toxic agent
and which is able to consume it as a substrate.
Finally, by using backpulse combinations (1 s/1 min) a stable
ux around 100 L/hm2 could be attained, with zero suspended solids
concentration and almost no phenolic compounds. Moreover,
backpulsing enabled maintaining successfully a constant permeate
ux over a period of several days.
Conidi et al. (2014) proposed an integrated membrane treatment
comprising MF (0.2 m) followed by UF (10 kDa MWCO) and a nal
MBR to achieve the reclamation and valorization of OMW from a
three-phase olive oil production process. They examined the efciency
of different membranes comprising at-sheet MF (cellulose acetate,
nylon and polyvinylidene uoride), at-sheet UF (regenerated
cellulose) and hollow ber UF (polysulfone).
The MF membrane permitted the removal of suspended solids, after
which low molecular weight polyphenolic compounds could be recov-
ered in the UF permeate stream. The UF permeate was nally driven
to a multiphase biocatalytic MBR, where the isomer of oleuropein-
aglycon was isolated from the phenolic fraction produced during the
former oleuropein hydrolysis reaction step, achieving a maximum
conversion of 45.7%.
5. OMW membrane-derived concentrate streams:
outputs and alternatives
Despite the fact that OMW can be effectively treated by means of
membrane technology, implying high volume reduction of the efu-
ent waste, a fraction of the initial volume, that is, the retentate or
concentrate streams, need further processing or treatment for their
nal output.
Some authors have pointed to valorization of the concentrates
through their reuse for different purposes as a feasible solution for re-
versing the overall costs balance of the proposed membrane processes.
Paraskeva et al. (2007) attained a volume recovery ratio between
8090% in the UF step of OMW-3, which thus resulted in 1020% in
volume of concentrate stream containing suspended solids and high
molecular weight compounds, including lipid components (90%) and
a considerable amount of phenolic compounds (~50%). These authors
suggested using the inorganic (P, Mg, K, metal traces) and organic
contents (hydrocarbons, nitrogenous compounds, organic acids,
polyalcohols) in the concentrate stream as plant nutrients in combina-
tion with other inorganic or organic fertilizers such as manure or sludge
10 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
from biological treatments of other types of wastes (Harvey et al., 2002;
Bais et al., 2002).
Similarly, Cassano et al. (2011, 2013) proposed the use of the UF
retentates (volume reduction factor equal to 3) containing high molec-
ular weight organic substances, for composting after polyphenolic
compounds depletion or subjection to anaerobic digestion for biogas
production. Otherwise, the NF retentate, rich in low molecular weight
polyphenolic compounds, was highlighted as suitable for cosmetic,
food and pharmaceutical industries as liquid, frozen, dried or lyophilized
formulations.
In an analogous line, very recently Zagklis et al. (2015) reported
around 25% concentrate volume after UF of OMW-3 (25 L), whereas
37.3% for NF and 26% for RO retentate streams. The RO concentrate
stream, containing the low-molecular-weight compounds (COD
65.5 g/L, TSS 1.7 g/L and TPh 2.1 g/L), was further treated through
non-ionic resins adsorption/desorption process with the aim of re-
covering phenols and their separation from carbohydrates. Finally,
the recovered phenolic compounds were concentrated by means of
vacuum evaporation, reaching a nal concentration of up to 378 g/L
in gallic acid equivalents containing 84.8 g/L hydroxytyrosol.
On another hand, in a recent study Cicci et al. (2013) have proposed
a different solution for the concentrate streams after membrane
treatment of OMW. Cicci et al. assessed the feasibility of using the
concentrate fractions obtained after the treatment of OMW-3 with
UF (concentrate COD 33.1 g/L) and NF (concentrate COD 20.1 g/L)
membranes-in-series process, the leftover fraction of the treated
wastewater representing 20% in volume, to produce low cost culture
media for growing the microalga Scenedesmus dimorphus 1237 and
the cyanobacterium Arthrospira platensis for a variety of uses ranging
from nutraceutical to biofuel feedstock. The investigation was car-
ried out in lab-scale photobioreactors. The presented results showed
that microalgae are able to grow in almost all the tested media,
although at a reduced rate with respect to their controls. The reduction
was mainly attributed to the presence of polyphenols.
6. Conclusions
The olive oil sector is one of the most important in the Countries of
the Mediterranean River Basin, but it is also relevant in others such as
France, Serbia and Montenegro, Macedonia, Cyprus, Egypt, Israel and
Jordan. Moreover, olive oil production is also becoming an emergent
agro-food industry in China and other countries such as the USA,
Australia and the Middle East. The treatment and reclamation of the ef-
uents generated by these industries, called olive mill efuents (OME),
is an environmental problem still to be resolved. The removal of
inorganic compounds from OME and also a variety of phytotoxic and
bacterial growth-inhibiting recalcitrant organic solutes cannot be
accomplished by conventional treatments and lead to cost-ineffective
results.
In the present work, a review on the actual state of the art of the
treatment and disposal of the OME from batch-press and continuous
two-phase and three-phase centrifugation systems by membranes is
addressed, comprising microltration, ultraltration, nanoltration
and reverse osmosis, as well as membrane bioreactors.
There are still some unresolved problems that slow down large-scale
membrane applications with respect to OMW management despite the
promising perspectives, similarly as those encountered in drinking
water production and also in wastewater treatment and many other
industries in relation to membranes. Undoubtedly, the main challenge
is the loss of membrane performance due to fouling issues.
The feed stream composition is the main responsible of ever chang-
ing ux values, and this is especially true for agricultural wastewater
streams treatment by membranes, since the entering feedstock compo-
sition is not constant during the campaign. Furthermore, the use of
batch membrane processes in order to limit the amount of required
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
membrane area, and thus saving investment costs, leads to sensible
feedstock changes during operation.
In this regard, direct treatment by membranes of raw efuents
has been reported to lead to rapid emergence of membrane fouling.
Appropriate fouling inhibition methods should be designed upstream
the membrane operation, in order to make the membrane processes
for wastewater stream treatment both technically and economically
feasible. Different integrated membrane treatment processes of the ef-
uents by-produced in olive mills by membranes are herein summa-
rized and discussed, with a focus on the appropriate pretreatments to
make the membrane operation performance stable and cost-efcient.
Acknowledgments
The Spanish Ministry of Science and Innovation is gratefully
acknowledged for having funded the projects CTQ2007-66178,
CTQ2010-21411 and CTM2014-61105-JIN, as well as the University
of Granada.
References
Agana, B.A., Reeve, D., Orbell, J.D., 2013. Performance optimization of a 5 nm TiO 2
ceramic membrane with respect to beverage production wastewater. Desalination
311, 162172.
Aimar, P., Bacchin, P., 2010. Slow colloidal aggregation and membrane fouling. J. Membr.
Sci. 360, 7076.
Akdemir, E.O., Ozer, A., 2009. Investigation of two ultraltration membranes for
treatment of olive oil mill wastewater. Desalination 249, 660666.
Aktas, E.S., Imre, S., Esroy, L., 2001. Characterization and lime treatment of olive mill
wastewater. Water Res. 35, 23362340.
Al-Malah, K., Azzam, M.O.J., Abu-Lail, N.I., 2000. Olive mills efuent (OME) wastewater
post-treatment using activated clay. Sep. Purif. Technol. 20, 225234.
Ammary, B.Y., 2005. Treatment of olive mill wastewater using an anaerobic sequencing
batch reactor. Desalination 177, 157165.
Annesini, M., Gironi, F., 1991. Olive oil mill efuent: ageing effects on evaporation
behavior. Water Res. 25, 11571960.
Bacchin, P., Aimar, P., Sanchez, V., 1996. Inuence of surface interaction on transfer during
colloid ultraltration. J. Membr. Sci. 115, 4963.
Bacchin, P., Aimar, P., Field, R.W., 2006. Critical and sustainable uxes: theory,
experiments and applications. J. Membr. Sci. 281, 4269.
Bais, H.P., Walker, T.S., Stermitz, F.R., Hufbauer, R.A., Vivanco, J.M., 2002. Enantiomeric-
dependent phytotoxic and antimicrobial activity of ()-catechin. A rhizosecreted
racemic mixture from spotted knapweed. Plant Physiol. 128, 11731179.
Belfort, G., Davis, R.H., Zydney, A.L., 1994. The behavior of suspensions and macromolec-
ular solutions in crossow microltration. J. Membr. Sci. 96, 158.
Beltran-Heredia, J., Garcia, J., 2005. Process integration: continuous anaerobic digestion
ozonation treatment of olive mill wastewater. Ind. Eng. Chem. Res. 44, 87508755.
Beltran-Heredia, J., Torregrosa, J., Garcia, J., 2001. Degradation of olive mill wastewater
by the combination of Fenton's reagent and ozonation processes with an aerobic
biological treatment. Water Sci. Technol. 44, 103108.
Bdalo, A., Gmez, J.L., Gmez, E., Mximo, F., Hidalgo, A.M., 2003. Application of
reverse osmosis to reduce pollutants present in industrial wastewater. Desalination
155, 101108.
Borsani, R., Ferrando, B., 1996. Ultraltration plant for olive vegetation waters by poly-
meric membrane batteries. Desalination 108, 281286.
Bouranis, D.L., Vlyssides, A.G., Drossopoulos, J.B., Karvouni, G., 1995. Some characteristics
of a new organic soil conditioner from the co-composting of olive oil processing
wastewater and solid residue. Commun. Soil Sci. Plant Anal. 26, 24612472.
Boussu, K., Kindts, C., Vandecasteele, C., Van der Bruggen, B., 2007. Applicability of
nanoltration in the carwash industry. Sep. Purif. Technol. 54 (2), 139146.
Calabr, V., Curcio, S., De Paola, M.G., Iorio, G., 2002. Membrane bioreactor for the enzy-
matic oxidation of polyphenols. Proceedings of ICOM 2002 Conference 712 July,
Toulouse.
Canepa, P., Marignetti, N., Rognoni, U., Calgari, S., 1988. Olive mills wastewater treatment
by combined membrane processes. Water Res. 22 (12), 14911494.
Caizares, P., Martinez, L., Paz, R., Saz, C., Lobato, J., Rodrigo, M.A., 2006. Treatment of
Fenton-refractory olive oil mill wastes by electrochemical oxidation with boron-
doped diamond anodes. J. Chem. Technol. Biotechnol. 81 (8), 13311337 (2006).
Caizares, P., Lobato, J., Paz, R., Rodrigo, M.A., Saz, C., 2007. Advanced oxidation processes
for the treatment of olive-oil mills wastewater. Chemosphere 67, 832838.
Caizares, P., Paz, R., Sez, C., Rodrigo, M.A., 2009. Costs of the electrochemical oxidation
of wastewaters: a comparison with ozonation and Fenton oxidation processes.
Environ. Manag. 90, 410420.
Cassano, A., Conidi, C., Drioli, E., 2011. Comparison of the performance of UF membranes
in olive mill wastewaters treatment. Water Res. 45, 31973204.
Cassano, A., Conidi, C., Giorno, L., Drioli, E., 2013. Fractionation of olive mill wastewaters
by membrane separation techniques. J. Hazard. Mater. 248, 185193.
Cegarra, J., Paredes, C., Roig, A., Bernal, M.P., Garca, D., 1996. Use of olive mill wastewater
compost for crop production. Int. Biodeterior. Biodegrad. 38 (34), 193203.
 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
Chatzisymeon, E., Xekoukoulotakis, N.P., Mantzavinos, D., 2009. Determination of key
operating conditions for the photocatalytic treatment of olive mill wastewaters.
Catal. Today 144, 143148.
Cheryan, M., 1998. Ultraltration and Microltration. Technomic Publishing Company
Inc., Lancaster, PA.
Cicci, A., Stoller, M., Bravi, M., 2013. Microalgal biomass production by using ultra- and
nanoltration membrane fractions of olive mill wastewater. Water Res. 47 (13),
47104718.
Conidi, C., Mazzei, R., Cassano, A., Giorno, L., 2014. Integrated membrane system for
the production of phytotherapics from olive mill wastewaters. J. Membr. Sci. 454,
322329.
Coskun, T., Debik, E., Demir, N.M., 2010. Treatment of olive mill wastewaters by
nanoltration and reverse osmosis membranes. Desalination 259 (2010), 6570.
Danellakis, D., Ntaikou, I., Kornaros, M., Dailianis, S., 2011. Olive oil mill wastewater
toxicity in the marine environment: alterations of stress indices in tissues of mussel
Mytilus galloprovincialis. Aquat. Toxicol. 101 (2), 358366.
Dhaouadi, H., Marrot, B., 2010. Olive mill wastewater treatment in a membrane bioreactor:
process stability and fouling aspects. Environ. Technol. 31 (7), 761770.
Dreosti, I.E., 2000. Antioxidant polyphenols in tea, cocoa, and wine. Nutrition. 16 (7/8),
692694.
Durn, N., Esposito, E., 2000. Potential applications of oxidative enzymes and
phenoloxidase-like compounds in wastewater and soil treatment: a review. Appl.
Catal. B: Environ. 28 (2), 8399.
Edwards, W., Bownes, R., Leukes, W.D., Jacobs, E.P., Sanderson, R., Rose, P.D., Burton, S.G.,
1999. A capillary membrane bioreactor using immobilized polyphenol oxidase for the
removal of phenols from industrial efuents. Enzyme Microb. Technol. 24 (3/4),
209217.
El-Abbassi, A., Khayet, M., Hadi, A., 2011. Micellar enhanced ultraltration process for
the treatment of olive mill wastewater. Water Res. 45, 45224530.
Ellouze, E., Tahri, N., Ben Amar, R., 2012. Enhancement of textile wastewater treatment
process using nanoltration. Desalination 286, 1623.
Epimakhov, V.N., Oleinik, M.S., Moskvin, L.N., 2004. Reverse osmosis ltration based water
treatment and special water purication for nuclear power systems. At. Energy 96
(4), 234240.
Espinasse, B., Bacchin, P., Aimar, P., 2002. On an experimental method to measure critical
ux in ultraltration. Desalination 146, 9196.
Field, R.W., Aimar, P., 1993. Ideal limiting uxes in ultraltration: comparison of various
theoretical relationships. J. Membr. Sci. 80, 107115.
Field, R.W., Pearce, G.K., 2011. Critical, sustainable and threshold uxes for membrane
ltration with water industry applications. Adv. Colloid Interf. Sci. 164, 3844.
Field, R.W., Wu, D., Howell, J.A., Gupta, B.B., 1995. Critical ux concept for microltration
fouling. J. Membr. Sci. 100, 259272.
Food and Agricultural Organization (FAO), 2003. Review of world water resources by
country. Water Reports 23, Rome, Italy.
Fountoulakis, M.S., Dokianakis, S.N., Kornaros, M.E., Aggelis, G.G., Lyberatos, G., 2002.
Removal of phenolics in olive mill wastewaters using the white-rot fungus Pleurotus
ostreatus. Water Res. 36, 47354744.
Garcia-Castello, E., Cassano, A., Criscuoli, A., Conidi, C., Drioli, E., 2010. Recovery and
concentration of polyphenols from olive mill wastewaters by integrated membrane
system. Water Res. 44, 38833892.
Garrido Hoyos, S.E., Martnez Nieto, L., Camacho Rubio, F., Ramos Cormenzana, A., 2002.
Kinetics of aerobic treatment of olive-mill wastewater (OMW) with Aspergillus
terreus. Process Biochem. 37 (10), 11691176.
Giacobbo, A., Oliveira, M., Duarte, E., Mira, H., Moura Bernardes, A., de Pinho, M., 2013.
Ultraltration based process for the recovery of polysaccharides and polyphenols
from winery efuents. Sep. Sci. Technol. 48, 438444.
Gonalves, M.R., Correia, J., Marques, I.P., 2012a. Electrochemical mineralization of
anaerobic digested olive mill wastewater. Water Res. 46 (13), 42174225.
Gonalves, M.R., Freitas, P., Marques, I.P., 2012b. Bioenergy recovery from olive mill
efuent in a hybrid reactor. Biomass Bioenergy 39, 253260.
Graas, P., Xekoukoulotakis, N.P., Mantzavinos, D., Diamadopoulos, E., 2010. Pilot
treatment of olive pomace leachate by vertical-ow constructed wetland and electro-
chemical oxidation: an efcient hybrid process. Water Res. 44 (9), 27732780.
Harvey, P.J., Campanella, B.F., Castro, P.M.L., Harms, H., Lichtfouse, E., Schffner, A.R.,
Smrcek, S., Werck-Reichhart, D., 2002. Phytoremediation of polyaromatic hydrocar-
bons, anilines and phenols. Environ. Sci. Pollut. Res. 9 (1), 2947.
Ho, W.S.W., Sirkar, K.K., 1992. Membrane Handbook. Chapman & Hall.
Hodaifa, G., Eugenia-Snchez, M., Snchez, S., 2008. Use of industrial wastewater from
olive-oil extraction for biomass production of Scenedesmus obliquus. Bioresour.
Technol. 99, 11111117.
Hodaifa, G., Ochando-Pulido, J.M., Ben-Driss-Alami, S., Rodriguez-Vives, S., Martinez-
Ferez, A., 2013a. Kinetic and thermodynamic parameters of iron adsorption onto
olive stones. Ind. Crop. Prod. 49, 526534.
Hodaifa, G., Ochando-Pulido, J.M., Rodriguez-Vives, S., Martinez-Ferez, A., 2013b. Optimi-
zation of continuous reactor at pilot scale for olive-oil mill wastewater treatment by
Fenton-like process. Chem. Eng. J. 220, 117124.
http://ec.europa.eu/programmes/horizon2020/
http://www.internationaloliveoil.org/
Iaquinta, M., Stoller, M., 2009. Optimization of a nanoltration membrane for tomato
industry wastewater treatment. Desalination 245, 314320.
Inan, H., Dimoglo, A., imek, H., Karpuzcu, M., 2004. Olive oil mill wastewater treatment
by means of electro-coagulation. Sep. Purif. Technol. 36 (1), 2331.
Ioannou, L.A., Michael, C., Vakondios, N., Drosou, K., Xekoukoulotakis, N.P.,
Diamadopoulos, E., Fatta-Kassinos, D., 2013. Winery wastewater purication by
reverse osmosis and oxidation of the concentrate by solar photo-Fenton. Sep.
Purif. Technol. 118, 659669.
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
11
Karaouzas, I., Skoulikidis, N.T., Giannakou, U., Albanis, T.A., 2011. Spatial and temporal
effects of olive mill wastewaters to stream macroinvertebrates and aquatic
ecosystems status. Water Res. 45 (19), 63346346.
Khou, S., Aloui, F., Sayadi, S., 2006. Treatment of olive oil mill wastewater by
combined process electro-Fenton reaction and anaerobic digestion. Water Res.
40, 20072016.
Korzenowski, C., Minhalma, M., Bernardes, A.M., Ferreira, J.Z., de Pinho, M.N., 2011.
Nanoltration for the treatment of coke plant ammoniacal wastewaters. Sep. Purif.
Technol. 76 (3), 303307.
Kougias, P.G., Kotsopoulos, T.A., Martzopoulos, G.G., 2014. Effect of feedstock composition
and organic loading rate during the mesophilic co-digestion of olive mill wastewater
and swine manure. Renew. Energy 69, 202207.
La, W.K., Shannak, B., Al-Shannag, M., Al-Anber, Z., Al-Hasan, M., 2009. Treatment of
olive mill wastewater by combined advanced oxidation and biodegradation. Sep.
Purif. Technol. 70 (2), 141146.
Le-Clech, P., Chen, V., Fane, T.A.G., 2006. Fouling in membrane bioreactors used in waste-
water treatment. J. Membr. Sci. 284 (12), 1753.
Lee, J.-W., Kwon, T.-O., Moon, I.-S., 2006. Performance of polyamide reverse osmosis
membranes for steel wastewater reuse. Desalination 189, 309322.
Lpez, J., Coello, M.D., Quiroga, J.M., 2006. Comparative studies of reverse osmosis
membranes for wastewater reclamation. Desalination 191, 137147.
Luo, J., Ding, L., Wan, Y., Jaffrin, M.Y., 2012. Threshold ux for shear-enhanced
nanoltration: experimental observation in dairy wastewater treatment. J. Membr.
Sci. 409, 276284.
Macedo, A., Duarte, E., Fragoso, R., 2015. Assessment of the performance of three
ultraltration membranes for fractionation of ovine second cheese whey. Int. Dairy
J. 48, 3137.
Mnttri, M., Nystrm, M., 2000. Critical ux in NF of high molar mass polysaccharides
and efuents from the paper industry. J. Membr. Sci. 170, 257273.
Marques, I.P., 2001. Anaerobic digestion treatment of olive mill wastewater for efuent
re-use in irrigation. Desalination 137, 233239.
Martnez Nieto, L., et al. (2008). Chemical and Biochemical Processes Technology
Research Group, University of Granada. Patent title P200600808, publication number
2.282.043, date 03/09/2008.
Martnez Nieto, L., Ben Driss Alami, S., Hodaifa, G., Faur, C., Rodrguez Vives, S., Gimnez
Casares, J.A., Ochando, J., 2010. Adsorption of iron on crude olive stones. Ind. Crop.
Prod. 32, 467471.
Martnez Nieto, L., Hodaifa, G., Rodrguez Vives, S., Gimnez Casares, J.A., Ochando, J.,
2011a. Degradation of organic matter in olive oil mill wastewater through homoge-
neous Fenton-like reaction. Chem. Eng. J. 173 (2), 503510.
Martnez Nieto, L., Hodaifa, G., Rodrguez Vives, S., Gimnez Casares, J.A., Ochando, J.,
2011b. Flocculationsedimentation combined with chemical oxidation process.
Clean: Soil, Air, Water 39 (10), 949955.
Mendoza, A., Hidalgo-Casado, F., Ruiz-Gmez, M.A., Martnez-Romn, F., Moyano-Prez,
M.J., Cert-Ventul, A., Prez-Camino, M.C., Ruiz-Mndez, M.V., 1996. Characteristics
of olive oils from rst and second centrifugation. Oil Grease 47, 163181.
Niaounakis, M., Halvadakis, C.P., 2006. Olive processing waste management
literature review and patent survey. 2nd ed. Waste Management Series 5.
Elsevier, pp. 2364.
Ntougias, S., Gaitis, F., Katsaris, P., Skoulika, S., Iliopoulos, N., Zervakis, G.I., 2013. The
effects of olives harvest period and production year on olive mill wastewater
properties evaluation of Pleurotus strains as bioindicators of the efuent's
toxicity. Chemosphere 92, 399405.
Ochando-Pulido, J.M.S., Rodriguez-Vives, J.M., Martinez-Ferez, A., 2012a. The effect of
permeate recirculation on the depuration of pretreated olive mill wastewater
through reverse osmosis membranes. Desalination 286, 145154.
Ochando-Pulido, J.M., Hodaifa, G., Rodriguez-Vives, S., Martinez-Ferez, A., 2012b. Impacts
of operating conditions on reverse osmosis performance of pretreated olive mill
wastewater. Water Res. 46 (15), 46214632.
Ochando-Pulido, J.M., Hodaifa, G., Martinez-Ferez, A., 2012c. Fouling inhibition upon
Fenton-like oxidation pretreatment for olive mill wastewater reclamation by
membrane process. Chem. Eng. Process. 62, 8998.
Ochando-Pulido, J.M., Stoller, M., Bravi, M., Martinez-Ferez, A., Chianese, A., 2012d. Batch
membrane treatment of olive vegetation wastewater from two-phase olive oil
production process by threshold ux based methods. Sep. Purif. Technol. 101, 3441.
Ochando-Pulido, J.M., Hodaifa, G., Victor-Ortega, M.D., Martinez-Ferez, A., 2014. Fouling
control by threshold ux measurements in the treatment of different olive mill
wastewater streams by membranes-in-series process. Desalination 343, 162168.
Ochando-Pulido, J.M., Verardo, V., Segura-Carretero, A., Martinez-Ferez, A., 2015.
Technical optimization of an integrated UF/NF pilot plant for conjoint batch
treatment of two-phase olives and olive oil washing wastewaters. Desalination
364, 8289.
Ognier, S., Wisniewski, C., Grasmick, A., 2004. Membrane bioreactor fouling in sub-critical
ltration conditions: a local critical ux concept. J. Membr. Sci. 229, 171177 (2004).
Papadimitriou, E.K., Chatjipavlidis, I., Balis, C., 1997. Application of composting to olive
mill wastewater treatment. Environ. Technol. 18 (1), 101107.
Papastefanakis, N., Mantzavinos, D., Katsaounis, A., 2010. DSA electrochemical treatment
of olive mill wastewater on Ti/RuO2 anode. J. Appl. Electrochem. 40 (4), 729737.
Paraskeva, P., Diamadopoulos, E., 2006. Technologies for olive mill wastewater (OMW)
treatment: a review. J. Chem. Technol. Biotechnol. 81, 14751485.
Paraskeva, C.A., Papadakis, V.G., Tsarouchi, E., Kanellopoulou, D.G., Koutsoukos, P.G.,
2007. Membrane processing for olive mill wastewater fractionation. Desalination
213, 218229.
Paugam, L., Diawara, C.K., Schlumpf, J.P., Jaouen, P., Qumneur, F., 2004. Transfer of
monovalent anions and nitrates especially through nanoltration membranes in
brackish water conditions. Sep. Purif. Technol. 40 (3), 237242.
12 J.M.O. Pulido / Science of the Total Environment xxx (2015) xxxxxx
Pizzichini, M., Russo, C., Di Meo, C., 2005. Purication of pulp and paper wastewater
with membrane technology for water reuse in a closed loop. Desalination 178,
351359.
Rice-Evans, C.A., Miller, N.J., Paganga, G., 1996. Structure-antioxidant activity relationships
of avonoids and phenolic acids. Free Rad. Biol. Med. 20 (7), 933956.
Rizzo, L., Lofrano, G., Grassi, M., Belgiorno, V., 2008. Pretreatment of olive mill
wastewater by chitosan coagulation and advanced oxidation processes. Sep.
Purif. Technol. 63 (3), 648653.
Russo, 2007. A new membrane process for the selective fractionation and total recovery
of polyphenols, water and organic substances from vegetation waters (VW).
J. Membr. Sci. 288, 239246.
Saad, M.A., 2005. Membrane desalination for the Arab world: overview and outlook. Arab
Water World 1.
Sacco, O., Stoller, M., Vaiano, V., Ciambelli, P., Chianese, A., Sannino, D., 2012. Photocatalytic
degradation of organic dyes under visible light on n-doped photocatalysts. Int.
J. Photoenergy 2012, 626759. http://dx.doi.org/10.1155/2012/626759.
Samodurov, A.N., Lysenko, S.E., Gromov, S.L., Panteleev, A.A., Fedoseeva, E.B., 2006. The
use of reverse osmosis technology for water treatment in power engineering.
Therm. Eng. 53 (6), 439443.
Sampaio, M.A., Gonalves, M.R., Marques, I.P., 2011. Anaerobic digestion challenge of raw
olive mill wastewater. Bioresour. Technol. 102, 1081010818.
Sarika, R., Kalogerakis, N., Mantzavinos, D., 2005. Treatment of olive mill efuents. Part II.
Complete removal of solids by direct occulation with poly-electrolytes. Environ. Int.
31, 297304.
Scoma, A., Berti, L., Fava, F., 2013. Effect of hydraulic retention time on biohydrogen and
volatile fatty acids production during acidogenic digestion of dephenolized olive
mill wastewaters. Biomass Bioenergy 48, 5158.
Stasinakis, A.S., Elia, I., Petalas, A.V., Halvadakis, C.P., 2008. Removal of total phenols from
olive-mill wastewater using an agricultural by-product, olive pomace. J. Hazard.
Mater. 160 (23), 408413.
Stoller, M., 2008. Technical optimization of a dual ultraltration and nanoltration pilot
plant in batch operation by means of the critical ux theory: a case study. Chem.
Eng. Process. J. 47 (7), 11651170.
Stoller, M., 2009. On the effect of occulation as pretreatment process and particle size
distribution for membrane fouling reduction. Desalination 240, 209217.
Stoller, M., 2011. Effective fouling inhibition by critical ux based optimization methods
on a NF membrane module for olive mill wastewater treatment. Chem. Eng. J. 168,
11401148.
Stoller, M., Bravi, M., 2010. Critical ux analyses on differently pretreated olive vegetation
wastewater streams: some case studies. Desalination 250, 578582.
Stoller, M., Chianese, A., 2006a. Optimization of membrane batch processes by means of
the critical ux theory. Desalination 191, 6270.
Stoller, M., Chianese, A., 2006b. Technical optimization of a batch olive wash wastewater
treatment membrane plant. Desalination 200 (13), 734736.
Stoller, M., Ochando-Pulido, J.M., 2012. Going from a critical ux concept to a threshold
ux concept on membrane processes treating olive mill wastewater streams.
Procedia Eng. 44, 607608.
Please cite this article as: Pulido, J.M.O., A review on the use of membrane technology and fouling control for olive mill wastewater treatment,
Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.09.151
Stoller, M., Bravi, M., Chianese, A., 2012. Threshold ux measurements of a nanoltration
membrane module by critical ux data conversion. Desalination http://dx.doi.org/10.
1016/j.desal.2012.11.013.
Stoller, M., De Caprariis, B., Cicci, A., Verdone, N., Bravi, M., Chianese, A., 2013a. About
proper membrane process design affected by fouling by means of the analysis of
measured threshold ux data. Sep. Purif. Technol. 114, 8389.
Stoller, M., Sacco, O., Sannino, D., Chianese, A., 2013b. Successful integration of membrane
technologies in a conventional purication process of tannery wastewater streams.
Membranes 3, 126135.
Taccari, M., Ciani, M., 2011. Use of Pichia fermentans and Candida sp. Strains for the
biological treatment of stored olive mill wastewater. Biotechnol. Lett. 33,
23852390.
Tekin, A.R., Cokun, A., 2000. Biogas production from olive pomace. Resour. Conserv.
Recycl. 30 (4), 301313.
Tezcan n, ., Uur, S., Koparal, A.S., tveren, .B., 2006. Electrocoagulation of olive
mill wastewaters. Sep. Purif. Technol. 52 (1), 136141.
Tezcan n, ., Altay, U., Koparal, A.S., Ogutveren, U.B., 2008. Complete treatment of olive
mill wastewaters by electrooxidation. Chem. Eng. J. 139, 445452.
Tu, K.L., Nghiem, L.D., Chivas, A.R., 2010. Boron removal by reverse osmosis membranes in
seawater desalination applications. Sep. Purif. Technol. 75 (2), 87101.
Turano, E., Curcio, S., De Paola, M.G., Calabr, V., Iorio, G., 2002. An integrated
centrifugationultraltration system in the treatment of olive mill wastewater.
J. Membr. Sci. 206, 519531.
Van der Bruggen, B., Vandecasteele, C., 2003. Removal of pollutants from surface water
and groundwater by nanoltration: overview of possible applications in the drinking
water industry. Environ. Pollut. 122, 435445.
Van der Bruggen, B., Everaert, K., Wilms, D., Vandecasteele, C., 2001. Application of
nanoltration for removal of pesticides, nitrate and hardness from ground water:
rejection properties and economic evaluation. J. Membr. Sci. 193, 239248.
Vyas, H.K., Bennett, R.J., Marshall, A.D., 2002. Performance of cross ow MF during
constant TMP and constant ux operations. Int. Diary J. 12, 473479.
Wei, X., Wang, Z., Fan, F., Wang, J., Wang, S., 2010. Advanced treatment of a complex
pharmaceutical wastewater by nanoltration: membrane foulant identication and
cleaning. Desalination 251, 167175.
Yiantsios, S.G., Karabelas, A.J., 2002. An assessment of the Silt Density Index based on RO
membrane colloidal fouling experiments with iron oxide particles. Desalination 15l,
229238.
Yin, N., Yang, G., Zhong, Z., Xing, W., 2011. Separation of ammonium salts from
coking wastewater with nanoltration combined with dialtration. Desalination
268, 233237.
Zagklis, D., Vavouraki, A., Kornaros, M., Paraskeva, C.A., 2015. Purication of olive mill
wastewater phenols through membrane ltration and resin adsorption/desorption.
J. Hazard. Mater. 285, 6976.
Zirehpour, A., Jahanshahi, M., Rahimpour, A., 2012. Unique membrane process integration
for olive oil mill wastewater purication. Sep. Purif. Technol. 96, 124131.